US2740794A - Synthesis of novel vanadium porphyrin - Google Patents
Synthesis of novel vanadium porphyrin Download PDFInfo
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- US2740794A US2740794A US445917A US44591754A US2740794A US 2740794 A US2740794 A US 2740794A US 445917 A US445917 A US 445917A US 44591754 A US44591754 A US 44591754A US 2740794 A US2740794 A US 2740794A
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- United States
- Prior art keywords
- refluxing
- admixture
- naphthalene
- vanadium
- precipitate
- Prior art date
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- Expired - Lifetime
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- 230000015572 biosynthetic process Effects 0.000 title description 3
- 238000003786 synthesis reaction Methods 0.000 title description 2
- YNZSKFFENDBGOV-UHFFFAOYSA-N [V].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [V].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 YNZSKFFENDBGOV-UHFFFAOYSA-N 0.000 title 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 30
- 238000010992 reflux Methods 0.000 claims description 17
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 14
- PCCQIRMWCXNVMM-UHFFFAOYSA-N 5,10,15,20-tetraphenyl-21,23-dihydroporphyrin vanadium Chemical compound C1(=CC=CC=C1)C1=C2C=CC(C(=C3C=CC(=C(C=4C=CC(=C(C5=CC=C1N5)C5=CC=CC=C5)N4)C4=CC=CC=C4)N3)C3=CC=CC=C3)=N2.[V] PCCQIRMWCXNVMM-UHFFFAOYSA-N 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 9
- 239000011343 solid material Substances 0.000 claims description 9
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 8
- 239000002026 chloroform extract Substances 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical class C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 238000001914 filtration Methods 0.000 description 6
- 229910052720 vanadium Inorganic materials 0.000 description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 6
- -1 aliphatic alcohols Chemical class 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical compound CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- ZYECOAILUNWEAL-NUDFZHEQSA-N (4z)-4-[[2-methoxy-5-(phenylcarbamoyl)phenyl]hydrazinylidene]-n-(3-nitrophenyl)-3-oxonaphthalene-2-carboxamide Chemical compound COC1=CC=C(C(=O)NC=2C=CC=CC=2)C=C1N\N=C(C1=CC=CC=C1C=1)/C(=O)C=1C(=O)NC1=CC=CC([N+]([O-])=O)=C1 ZYECOAILUNWEAL-NUDFZHEQSA-N 0.000 description 1
- 235000009470 Theobroma cacao Nutrition 0.000 description 1
- 244000240602 cacao Species 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T436/00—Chemistry: analytical and immunological testing
- Y10T436/10—Composition for standardization, calibration, simulation, stabilization, preparation or preservation; processes of use in preparation for chemical testing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T436/00—Chemistry: analytical and immunological testing
- Y10T436/10—Composition for standardization, calibration, simulation, stabilization, preparation or preservation; processes of use in preparation for chemical testing
- Y10T436/109163—Inorganic standards or controls
Definitions
- The. presentinvention may .be. ibrieflydescribed asr vanadium tetraphenyl porphyrinehaving' the. structural formula:
- the present' invention involves amethodfor producingwanadium tetraphenyl, porphyrinhavingatheastruc- 1 tural formula described supraby "reactingiyanadiumtpentoxide and hydrochloric acid under refluxing conditions in which an aliphatic alcohol is added to the refluxing mixture. The refluxing is continued until the color of the mixture changes from dark red to bright green and finally to a dark blue or deep blue. Thereafter the pH of the solution is adjusted in a range of about 6.0 to about 7.0 whereby a precipitate is formed. The precipitate is recovered, for example, by filtration and then formed into a second admixture with naphthalene and tetraphenyl porphyrin.
- the second mixture is refluxed and a bright red melt is obtained.
- the melt is admixed with distilled water to form a third admixture from which solid material is recovered by filtration. Thereafter the recovered material is extracted in sequence with aliphatic alcohol or acetone to remove naphthalene and with chloroform to form a chloroform extract.
- the alcohol employed in the practice of the present invention is preferably ethanol, but other aliphatic alcohols, such as methyl alcohol, isopropyl and propyl alcohols as well as the butyl alcohols may be used.
- the pH of the solution may be adjusted by employing saturated sodium carbonate and the like.
- the aromatic hydrocarbon which is used to extract the residue is preferably benzene but may be any low boiling aromatic hydrocarbon, such as toluene, ortho, meta or paraxylene or ethyl benzene, and the like.
- the solid material is then recovered by filtering the mixture from the second reaction vessel and the solid material is broken up into lumps or granular bodies.
- the granular bodies are then extracted with ethanol or acetone for several hours in an extractor similar in structure to the Soxhlet extractor, for approximately 3 to 6 hours.
- the remaining material is extracted with chloroform in a similar extraction apparatus to form a chloroform extract which is recovered.
- the chloroform extract is evaporated to dryness to form and recover a residue. This residue is then fractionally extracted with aromatic hydrocarbons, such as benzene and the like.
- the material which is less soluble than benzene is the vanadium tetraphenyl porphyrin having the structural formula set out supra. This is a solid phase which may be sublimed at 880 F. under reduced pressure; for example, 1 micron to obtain the vanadium tetraphenyl porphyrin as octahedra having a dark redviolet coloration.
- The'vanadium tetraphenyl porphyrin having the structural formula given supra sublimes at a temperature of 830 to 880 F. at l to 5 microns and is characterized by having a very high melting point, limited solubility in organic solvents, and the following analysis: Calculated for CMHZBNQOVZC, 77.75; H, 4.15; N, 8.24; V, 7.50%. Found: C, 77.73; H, 4.36; N, 8.64; V, 7.48%.
- This compound is solid at 460 C. which is higher than any known compound given in the handbook ref erences.
- the high sublimation temperature indicates thermal stability.
- the vanadium tetraphenyl porphyrin is a new compound not found in nature and has the structural formula as given supra wherein the vanadium is linked to the nitrogen by co-valent bonds with the phenyl groups being disposed in the structure as shown attached to the carbon atoms.
- a method for producing vanadium tetraphenyl porphyrin which comprises refluxing a mixture of a minor amount of vanadium pentoxide and a major amount of hydrochloric acid, adding a saturated aliphatic alcohol containing 1 to 4 carbon atoms to the refluxing mixture and continuing the refluxing until a solution having a clear, bright, deep blue color develops, adjusting the pH of the solution to a pH in the range from about 6.0 to about 7.0 to form a precipitate, recovering the precipitate in the substantial absence of air, forming a sec- 0nd admixture of the precipitate with naphthalene and tetraphenyl porphyrin, said naphthalene and tetraphenyl porphyrin being in the ratio of at least about 6 to 1, refluxing the second admixture until a bright red meltis obtained, admixing the melt with distilled water to form a third admixture, recovering solid material from the third admixture, extracting the solid
- a method for producing vanadium tetraphenyl porphyrin which comprises refluxing a mixture of vanadium pentoxide and concentrated hydrochloric acid in a ratio of approximately 1 part of vanadium pentoxide, to approximately 5 parts of acid, adding ethanol tothe refluxing mixture and conducting the refluxing operation fora sufiicient length of time until the refluxing mixture goes through a series of color changes from dark red to bright green and finally to a clear, bright,
Description
2,740,194 SYNTHESIS'OFNOVEL vANxmurvrroRPnYmNi WillardH; Bonner, In, Baytown flTexa-assi'gnon bymesne assignments, to Ess'o Research and=-.Engineei ing,. Comparty, Elizabeth, N. 3;, as corporationeof Delaware? NUDiaWing. Application'litl3326;I954;
Serial Noa 445 91 7 5- Claims (Cl; 260-314);.-
The. present invention isdirected to. as novel. porphyrin of vanadium.. More .particularly ndhe.inventionistdie rected-to-a novel vanadium compound=and a method-.of preparing. same:
The. presentinvention may .be. ibrieflydescribed asr vanadium tetraphenyl porphyrinehaving' the. structural formula:
The present' invention involves amethodfor producingwanadium tetraphenyl, porphyrinhavingatheastruc- 1 tural formula described supraby "reactingiyanadiumtpentoxide and hydrochloric acid under refluxing conditions in which an aliphatic alcohol is added to the refluxing mixture. The refluxing is continued until the color of the mixture changes from dark red to bright green and finally to a dark blue or deep blue. Thereafter the pH of the solution is adjusted in a range of about 6.0 to about 7.0 whereby a precipitate is formed. The precipitate is recovered, for example, by filtration and then formed into a second admixture with naphthalene and tetraphenyl porphyrin. The second mixture is refluxed and a bright red melt is obtained. The melt is admixed with distilled water to form a third admixture from which solid material is recovered by filtration. Thereafter the recovered material is extracted in sequence with aliphatic alcohol or acetone to remove naphthalene and with chloroform to form a chloroform extract.
tracted to leave a solid phase from which the vanadium tetraphenyl porphyrin is obtained by sublimation.
The alcohol employed in the practice of the present invention is preferably ethanol, but other aliphatic alcohols, such as methyl alcohol, isopropyl and propyl alcohols as well as the butyl alcohols may be used.
The pH of the solution may be adjusted by employing saturated sodium carbonate and the like.
The aromatic hydrocarbon which is used to extract the residue is preferably benzene but may be any low boiling aromatic hydrocarbon, such as toluene, ortho, meta or paraxylene or ethyl benzene, and the like.
The novel vanadium tetraphenyl porphyrin having the Theextract is dried to a residue which is fractionally ex 2,740,794 Patented Apr: 3,- 1956 Example" 10 parts-of. vanadium. pentoxidewere: placed: in.- a' "reaction. vessel. to-which 50 partsyof concentratedhydro"- chlorio acid. were added. The mixture of-vanadium pentoxide and concentrated hydrochlorid -acid-was re fluxedforabout:15-minutes andthereafterl'-two parts of ethanol werev added and refluxingtcontinuedtfor- -:20---more minutes. During these operationsthe: ma terial's-in the reactionvessel go. through a SBIiCSTOfi-CO'IOI changes: dark .red bright:green; and a clean-bright, dark blue color: In
the synthesis-oi the novel compound of: the presentinvention,. it. isr important that= the-mixture develop the clean, bright, deeper dark blue colorwhich mustihave no'traee of green in itor be substantially freeof greenicoloration.
Thereafter. to the mixture in. the :reaetion vesselk'sa'turated aqueous-sodium carbonate solution-is added until the pH- of. thesolution is between .about-- 6sandaboutfl'. This causes the formation of a lightcocoascolored precipitate: Thisprecipitate is recovered, 1 for examplegi by filtration. and washed. with 100 partsoi, distilled-water in. tvv ct 5.0- part.increments.- The water. washed precipitate: is themwashedwith 50 parts of absolute ethanoli in two 25 part. increments. Theprecipitatei is driedtand immediately removed r from theqfilter-with minimum ex- .posureto and in the substantial absenceof free-oxygen,
suchtas air.: The washed precipitate-is then; placed in a. second... reaction .vessel containing approximately 1 3 0-80 parts. of naphthalene and approximately .5. parts-of= tetraphenyl. porphyrin. A ratio-of naphthalene toItetrapheny-l porphyrindn the range from about-- 6'to about- 15:1; may
be used with satisfactory results being; obtained at a ratiomof. at least about; '6: The mixturein the :second reactionwvesself ist refluxed? at---about 21 7 C. until-a bright red melt is obtained. The meltviss poured into approximately 500 parts of distilled water while stirring.
The solid material is then recovered by filtering the mixture from the second reaction vessel and the solid material is broken up into lumps or granular bodies. The granular bodies are then extracted with ethanol or acetone for several hours in an extractor similar in structure to the Soxhlet extractor, for approximately 3 to 6 hours. When removal of naphthalene is complete by solution in the ethanol, the remaining material is extracted with chloroform in a similar extraction apparatus to form a chloroform extract which is recovered. The chloroform extract is evaporated to dryness to form and recover a residue. This residue is then fractionally extracted with aromatic hydrocarbons, such as benzene and the like. The material which is less soluble than benzene is the vanadium tetraphenyl porphyrin having the structural formula set out supra. This is a solid phase which may be sublimed at 880 F. under reduced pressure; for example, 1 micron to obtain the vanadium tetraphenyl porphyrin as octahedra having a dark redviolet coloration.
It was found that the product obtained, as has been described, contained approximately 7.50% vanadium and was obtained in yields of about based on the theoretical yields.
The'vanadium tetraphenyl porphyrin having the structural formula given supra sublimes at a temperature of 830 to 880 F. at l to 5 microns and is characterized by having a very high melting point, limited solubility in organic solvents, and the following analysis: Calculated for CMHZBNQOVZC, 77.75; H, 4.15; N, 8.24; V, 7.50%. Found: C, 77.73; H, 4.36; N, 8.64; V, 7.48%.
This compound is solid at 460 C. which is higher than any known compound given in the handbook ref erences. The high sublimation temperature indicates thermal stability.
The vanadium tetraphenyl porphyrin is a new compound not found in nature and has the structural formula as given supra wherein the vanadium is linked to the nitrogen by co-valent bonds with the phenyl groups being disposed in the structure as shown attached to the carbon atoms.
The nature and objects of the present inventionhaving been completely described and illustrated, what I wish to claim as new and useful and to secure by Letters Patent is: y
1. A method for producing vanadium tetraphenyl porphyrin which comprises refluxing a mixture of a minor amount of vanadium pentoxide and a major amount of hydrochloric acid, adding a saturated aliphatic alcohol containing 1 to 4 carbon atoms to the refluxing mixture and continuing the refluxing until a solution having a clear, bright, deep blue color develops, adjusting the pH of the solution to a pH in the range from about 6.0 to about 7.0 to form a precipitate, recovering the precipitate in the substantial absence of air, forming a sec- 0nd admixture of the precipitate with naphthalene and tetraphenyl porphyrin, said naphthalene and tetraphenyl porphyrin being in the ratio of at least about 6 to 1, refluxing the second admixture until a bright red meltis obtained, admixing the melt with distilled water to form a third admixture, recovering solid material from the third admixture, extracting the solid material with a solvent selected from the group consisting of the aliphatic alcohols and acetone to remove naphthalene, extracting remaining solid material with chloroform to form a chloroform extract, drying the chloroform extract to form a residue, fractionally exteracting the residue with a low boiling aromatic hydrocarbon to form an aromatic hydrocarbon soluble phase and a solid v 3. A method in accordance with claim 1 in which the. bright red melt is obtained by refluxing the second phase, and subliming said solid phase to obtain vanadium tetraphenyl porphyrin therefrom.
2. A method in accordance with claim 1 in which the aliphatic alcohol is ethanol and the aromatic hydrocarbon is benzene.
admixture at a temperature of about 217 C.
4. A method for producing vanadium tetraphenyl porphyrin which comprises refluxing a mixture of vanadium pentoxide and concentrated hydrochloric acid in a ratio of approximately 1 part of vanadium pentoxide, to approximately 5 parts of acid, adding ethanol tothe refluxing mixture and conducting the refluxing operation fora sufiicient length of time until the refluxing mixture goes through a series of color changes from dark red to bright green and finally to a clear, bright,
deep blue substantially free of green coloration, neu-' tralizing the refluxed mixture to a pH in the range'from about 6.0 to about 7.0 by adding saturated aqueous sodium carbonate'solution to the neutralized mixture to form a precipitate having a light cocoa color, filtering the precipitate and washing same in sequence with distilled water and ethanol, removing the Water and ethanol from the washed precipitate in the substantial absence of air, forming a second admixture of the washed precipitate with naphthalene and tetraphenyl porphyrin, said naphthalene and tetraphenyl porphyrin being in a ration of at least about 6:1, refluxing the second admixture at a temperature of about 217 C. until a bright red melt is obtained, admixing the melt with water and filtering the resulting admixture to obtain a granular body, extracting the granular body with a solvent selected from the group consisting of ethanol and acetone to remove naphthalene therefrom and then extracting the naphthalene-free body with chloroform to form an extract comprising a solution of chloroform soluble materials removed from the body, removing chloroform by evaporating the chloroform solution to form a residue, fractionally extracting the residue with benzene to form a benzene phase and an extract residue phase, and then subliming the extract residue phase at a temperature of about 830 to 880 F. under reduced pressure to obtain vanadium tetraphenyl porphyrin.
5. A method in accordance with claim 4 in which the ratio of naphthalene to tetraphenyl porphyrin is in the range from about 6:1 to about :1.
References Cited in the file of this patent Chem. Abst.: vol 5, p. 3293; vol. 24, p. 2204; vol. 27, p. 1054; vol. 28, p. 3694; vol. 29, p. 2699.
Claims (1)
1. A METHOD FOR PRODUCING VANADIUM TETRAPHENYL PORPHYRIN WHICH COMPRISES REFLUXING A MIXTURE OF A MINOR AMOUNT OF VANADIUM PENTOXIDE AND A MAJOR AMOUNT OF HYDROCHLORIC ACID, ADDING A SATURATED ALIPHATIC ALCOHOL CONTAINING 1 TO 4 CARBON ATOMS TO THE REFLUXING MIXTURE AND CONTINUING THE REFLUXING UNTIL A SOLUTION HAVING A CLEAR, BRIGHT, DEEP BLUE COLOR DEVELOPS, ADJUSTING THE PH OF THE SOLUTION TO A PH IN THE RANGE FROM ABOUT 6.0 TO ABOUT 7.0 TO FORM A PRECIPITATE, RECOVERING THE PRECIPITATE IN THE SUBSTANTIAL ABSENCE OF AIR, FORMING A SECOND ADMIXTURE OF THE PRECIPITATE WITH NAPHTHALENE AND TETRAPHENYL PORPHYRIN, SAID NAPHTHALENE AND TETRAPHENYL PORPHYRIN BEING IN THE RATIO OF AT LEAST ABOUT 6 TO 1, REFLUXING THE SECOND ADMIXTURE UNTIL A BRIGHT RED MELT IS OBTAINED, ADMIXING THE MELT WITH DISTILLED WATER TO FORM A THIRD ADMIXTURE, RECOVERING SOLID MATERIAL FROM THE THIRD ADMIXTURE, EXTRACTING THE SOLID MATERIAL WITH A SOLVENT SELECTED FROM THE GROUP CONSISTING OF THE ALIPHATIC ALCOHOLS AND ACETONE TO REMOVE NAPHTHALENE, EXTRACTING REMAINING SOLID MATERIAL WITH CHLOROFORM TO FORM A CHLOROFORM EXTRACT, DRYING THE CHLOROFORM EXTRACT TO FORM A RESIDUE, FRACTIONALLY EXTERACTING THE RESIDUE WITH A LOW BOILING AROMATIC HYDROCARBON TO FORM AN AROMATIC HYDROCARBON SOLUBLE PHASE AND A SOLID PHASE, AND SUBLIMING SAID SOLID PHASE TO OBTAIN VANADIUM TETRAPHENYL PORPHYRIN THEREFROM.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US445917A US2740794A (en) | 1954-07-26 | 1954-07-26 | Synthesis of novel vanadium porphyrin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US445917A US2740794A (en) | 1954-07-26 | 1954-07-26 | Synthesis of novel vanadium porphyrin |
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| Publication Number | Publication Date |
|---|---|
| US2740794A true US2740794A (en) | 1956-04-03 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US445917A Expired - Lifetime US2740794A (en) | 1954-07-26 | 1954-07-26 | Synthesis of novel vanadium porphyrin |
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| Country | Link |
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| US (1) | US2740794A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2867626A (en) * | 1956-05-18 | 1959-01-06 | Gulf Research Development Co | Synthesis of porphyrin vanadium complexes |
| US4885114A (en) * | 1987-04-22 | 1989-12-05 | Barnes Engineering Co. | Metallized tetra((meso)-5-methyl-2-thiophene)porphines, platinum (5-bromo octaethylporphine) and optical filters containing same |
| US4992257A (en) * | 1988-03-11 | 1991-02-12 | Efamol Holdings Plc | Dihydroporphyrins and method of treating tumors |
| US5236914A (en) * | 1988-06-02 | 1993-08-17 | Centre National De La Recherche Scientifique (Cnrs) | Derivatives of metalloporphyrins and application thereof for therapeutic purposes and in preparing hybrid molecules |
| US5262532A (en) * | 1991-07-22 | 1993-11-16 | E.R. Squibb & Sons, Inc. | Paramagnetic metalloporphyrins as contrast agents for magnetic resonance imaging |
-
1954
- 1954-07-26 US US445917A patent/US2740794A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2867626A (en) * | 1956-05-18 | 1959-01-06 | Gulf Research Development Co | Synthesis of porphyrin vanadium complexes |
| US4885114A (en) * | 1987-04-22 | 1989-12-05 | Barnes Engineering Co. | Metallized tetra((meso)-5-methyl-2-thiophene)porphines, platinum (5-bromo octaethylporphine) and optical filters containing same |
| US4992257A (en) * | 1988-03-11 | 1991-02-12 | Efamol Holdings Plc | Dihydroporphyrins and method of treating tumors |
| US5236914A (en) * | 1988-06-02 | 1993-08-17 | Centre National De La Recherche Scientifique (Cnrs) | Derivatives of metalloporphyrins and application thereof for therapeutic purposes and in preparing hybrid molecules |
| US5262532A (en) * | 1991-07-22 | 1993-11-16 | E.R. Squibb & Sons, Inc. | Paramagnetic metalloporphyrins as contrast agents for magnetic resonance imaging |
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